Role of image charges in ionic liquid confined between metallic interfaces.

The peculiar properties of ionic liquids in confinement have not only become essential for energy storage, catalysis and tribology, but still pose fundamental questions. Recently, an anomalous liquid-solid phase transition has been observed in atomic force microscopy experiments for 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), the transition being more pronounced for metallic surfaces. Image charges have been suggested as the key element driving the anomalous freezing. Using atomistic molecular dynamics simulations, we investigate the impact of image charges on structure, dynamics and thermodynamics of [BMIM][BF4] confined between gold electrodes. Our results not only unveil…

Oxide/water interfaces: how the surface chemistry modifies interfacial water properties

The organization of water at the interface with silica and alumina oxides is analysed using density functional theory-based molecular dynamics simulation (DFT-MD). The interfacial hydrogen bonding is investigated in detail and related to the chemistry of the oxide surfaces by computing the surface charge density and acidity. We find that water molecules hydrogen-bonded to the surface have different orientations depending on the strength of the hydrogen bonds and use this observation to explain the features in the surface vibrational spectra measured by sum frequency generation spectroscopy. In particular, 'ice-like' and 'liquid-like' features in these spectra are interpreted as the result o…

The Fluorite/Water Interfaces: Structure and Spectroscopy from First Principles Simulations

Despite its relevance to industrial, environmental and medical application, the fluorite/water interface still lacks a microscopic/atomistic characterization. In this contribution we provide the first atomistic description of such interface using first principles molecular dynamics simulations. Our models, which explore a wide range of pH, are able to provide a rational of the recent vibrational spectroscopy experiments. In particular we find that at neutral pH the water at the interface is disordered, in agreement with the experimental data, and explaining why no Vibrational Sum Frequency Generation (VSFG) signal is recorded. At high pH, OH groups which localize at the interface are respon…

Frontiers in molecular simulation of solvated ions, molecules and interfaces.

This themed collection is a collection of articles on frontiers in molecular simulation of solvated ions, molecules and interfaces.

Understanding the microscopic origin of gold nanoparticle anisotropic growth from molecular dynamics simulations.

We use molecular dynamics simulations in order to understand the microscopic origin of the asymmetric growth mechanism in gold nanorods. We provide the first atomistic model of different surfaces on gold nanoparticles in a growing electrolyte solution, and we describe the interaction of the metal with the surfactants, namely, cetyltrimethylammonium bromide (CTAB) and the ions. An innovative aspect is the inclusion of the role of the surfactants, which are explicitly modeled. We find that on all the investigated surfaces, namely, (111), (110), and (100), CTAB forms a layer of distorted cylindrical micelles where channels among micelles provide direct ion access to the surface. In particular,…

Heterogeneous Interactions between Gas-Phase Pyruvic Acid and Hydroxylated Silica Surfaces: A Combined Experimental and Theoretical Study

The adsorption of gas-phase pyruvic acid (CH3COCOOH) on hydroxylated silica particles has been investigated at 296 K using transmission Fourier transform infrared (FTIR) spectroscopy and theoretical simulations. Under dry conditions (<1% relative humidity, RH), both the trans-cis (Tc) and trans-trans (Tt) pyruvic acid conformers are observed on the surface as well as the (hydrogen bonded) pyruvic acid dimer. The detailed surface interactions were further understood through ab initio molecular dynamics simulations. Under higher relative humidity conditions (above 10% RH), adsorbed water competes for surface adsorption sites. Adsorbed water is also observed to change the relative populations …

From Gold Nanoseeds to Nanorods: The Microscopic Origin of the Anisotropic Growth

Directly manipulating and controlling the size and shape of metal nanoparticles is a key step for their tailored applications. In this work, molecular dynamics simulations were applied to understand the microscopic origin of the asymmetric growth mechanism in gold nanorods. Different factors influencing the growth were selectively included in the models to unravel the role of the surfactants and ions. In the early stage of the growth, when the seed is only a few nanometers large, a dramatic symmetry breaking occurs as the surfactant layer preferentially covers the (100) and (110) facets, leaving the (111) facets unprotected. This anisotropic surfactant layer in turn promotes anisotropic gro…

The nanoscale structure of the Pt-water double layer under bias revealed

The nanoscopic mass and charge distribution within the double layer at electrified interfaces plays a key role in electrochemical phenomena of huge technological relevance for energy production and conversion. However, in spite of its importance, the nanoscopic structure of the double layer and its response to an applied potential is still almost entirely unknown, even for Pt-water, the most fundamental electrochemical interface. Using a general ab initio methodology which advances previous models towards a dynamic and more realistic description of an electrode/electrolyte interface, we simulate for the first time the nanoscopic structure of the Pt-water double layer and its response to an …

The role of halide ions in the anisotropic growth of gold nanoparticles: a microscopic, atomistic perspective

We provide a microscopic view of the role of halides in controlling the anisotropic growth of gold nanorods through a combined computational and experimental study. Atomistic molecular dynamics simulations unveil that Br− adsorption is not only responsible for surface passivation, but also acts as the driving force for CTAB micelle adsorption and stabilization on the gold surface in a facet-dependent way. The partial replacement of Br− by Cl− decreases the difference between facets and the surfactant density. Finally, in the CTAC solution, no halides or micellar structures protect the gold surface and further gold reduction should be uniformly possible. Experimentally observed nanoparticle'…

Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles

International audience; Nanophase segregation of a bi-component thiol self-assembled monolayer is predicted using atomistic molecular dynamics simulations and experimentally confirmed. The simulations suggest the formation of domains rich in acid-terminated chains, on one hand, and of domains rich in amide-functionalized ethylene glycol oligomers, on the other hand. In particular, within the amide-ethylene glycol oligomers region, a key role is played by the formation of inter-chain hydrogen bonds. The predicted phase segregation is experimentally confirmed by the synthesis of 35 and 15 nm gold nanoparticles functionalized with several binary mixtures of ligands. An extensive study by trans…

The Silica-Water Interface: How the Silanols Determine the Surface Acidity and Modulate the Water Properties.

Silica is the most abundant metal oxide and the main component of the Earth's crust. Its behavior in contact with water plays a critical role in a variety of geochemical and environmental processes. Despite its key role, the details of the aqueous silica interface at the microscopic molecular level are still elusive. Here we provide such a detailed understanding of the molecular behavior of the silica-water interface, using density functional theory based molecular dynamics (DFTMD) simulations, where a consistent treatment of the electronic structure of solvent and surface is provided. We have calculated the acidity of the silanol groups at the interface directly from the DFTMD simulations,…

A new force field including charge directionality for TMAO in aqueous solution

We propose a new force field for trimethylamine N-oxide (TMAO), which is designed to reproduce the long-lived and highly directional hydrogen bond between the TMAO oxygen (OTMAO) atom and surrounding water molecules. Based on the data obtained by ab initio molecular dynamics simulations, we introduce three dummy sites around OTMAO to mimic the OTMAO lone pairs and we migrate the negative charge on the OTMAO to the dummy sites. The force field model developed here improves both structural and dynamical properties of aqueous TMAO solutions. Moreover, it reproduces the experimentally observed dependence of viscosity upon increasing TMAO concentration quantitatively. The simple procedure of the…

Multiscale modeling on biological systems

On the origin of controlled anisotropic growth of monodisperse gold nanobipyramids

We elucidate the crucial role of the cetyl trimethylammonium bromide (CTAB) surfactant in the anisotropic growth mechanism of gold nano-bipyramids, nano-objects with remarkable optical properties and high tunability. Atomistic molecular dynamics simulations predict different surface coverages of the CTAB (positively charged) heads and their (bromide) counterions as function of the gold exposed surfaces. High concentration of CTAB surfactant promotes formation of gold nanograins in solution that work as precursors for the smooth anisotropic growth of more elongated nano-bipyramidal objects. Nanobipyramids feature higher index facets with respect to nanorods, allowing higher CTAB coverages th…

Molecular Dynamics Simulations of SFG Librational Modes Spectra of Water at the Water–Air Interface

At the water–air interface, the hydrogen-bond network of water molecules is interrupted, and accordingly, the structure and dynamics of the interfacial water molecules are altered considerably compared with the bulk. Such interfacial water molecules have been studied by surface-specific vibrational sum-frequency generation (SFG) spectroscopy probing high-frequency O–H stretch and H–O–H bending modes. In contrast, the low-frequency librational mode has been much less studied with SFG. Because this mode is sensitive to the hydrogen-bond connectivity, understanding the librational mode of the interfacial water is crucial for unveiling a microscopic view of the interfacial water. Here, we compu…

Unravelling the GLY-PRO-GLU tripeptide induced reconstruction of the Au(110) surface at the molecular scale

International audience; The adsorption of GLY-PRO-GLU tripeptide on Au(110) is investigated within the frame of all atom classical mechanics simulations and Density Functional Theory, focusing on the surface reconstruction. It is shown that the tripeptide adsorption reorganizes and restructures the Au(110) surface. A mechanism for the surface restructuration is proposed for both the neutral and zwitterionic form of the peptide at room temperature in Ultra High Vacuum. Diverse residues may be involved in the Au atoms displacement, and in particular glutamic acid, triggering a double proton transfer and the formation of a zwitter ionic state, is found to be responsible for the triggering of t…

Water orientation and hydrogen-bond structure at the fluorite/water interface

AbstractWater in contact with mineral interfaces is important for a variety of different processes. Here, we present a combined theoretical/experimental study which provides a quantitative, molecular-level understanding of the ubiquitous and important CaF2/water interface. Our results show that, at low pH, the surface is positively charged, causing a substantial degree of water ordering. The surface charge originates primarily from the dissolution of fluoride ions, rather than from adsorption of protons to the surface. At high pH we observe the presence of Ca-OH species pointing into the water. These OH groups interact remarkably weakly with the surrounding water and are responsible for the…

The amorphous silica-liquid water interface studied by ab initio molecular dynamics (AIMD): local organization in global disorder

International audience; The structural organization of water at a model of amorphous silica-liquid water interface is investigated by ab initio molecular dynamics (AIMD) simulations at room temperature. The amorphous surface is constructed with isolated, H-bonded vicinal and geminal silanols. In the absence of water, the silanols have orientations that depend on the local surface topology (i.e. presence of concave and convex zones). However, in the presence of liquid water, only the strong inter-silanol H-bonds are maintained, whereas the weaker ones are replaced by H-bonds formed with interfacial water molecules. All silanols are found to act as H- bond donors to water. The vicinal silanol…

Bimodal Acidity at the Amorphous Silica/Water Interface

International audience; Understanding the microscopic origin of the acid base behavior of mineral surfaces in contact with water is still a challenging task, for both the experimental and the theoretical communities. Even for a relatively simple material, such as silica, the origin of the bimodal acidity behavior is still a debated topic. In this contribution we calculate the acidity of single sites on the humid silica surface represented by a model for the hydroxylated amorphous surface. Using a thermodynamic integration approach based on ab initio molecular dynamics, we identify two different acidity values. In particular, some convex geminals and some type of vicinals are very acidic (pK…

Interaction of Charged Amino-Acid Side Chains with Ions: An Optimization Strategy for Classical Force Fields

Many well-established classical biomolecular force fields, fitted on the solvation properties of single ions, do not necessarily describe all the details of ion pairing accurately, especially for complex polyatomic ions. Depending on the target application, it might not be sufficient to reproduce the thermodynamics of ion pairing, but it may also be necessary to correctly capture structural details, such as the coordination mode. In this work, we analyzed how classical force fields can be optimized to yield a realistic description of these different aspects of ion pairing. Given the prominent role of the interactions of negatively charged amino-acid side chains and divalent cations in many …

The role of halide ions in the anisotropic growth of gold nanoparticles: a microscopic, atomistic perspective† †Electronic supplementary information (ESI) available: Solvation structure of halides, electrostatic potentials at the interface, halide ions on the Au(111) surface in water, density profiles and electrostatic potential profiles for different CTAB/CTAC systems and conversion of the plasmon shift to the layer thickness. See DOI: 10.1039/c6cp01076h Click here for additional data file.

We provide a microscopic view of the role of halides in controlling the anisotropic growth of gold nanorods through a combined computational and experimental study.

A set-up for simultaneous measurement of second harmonic generation and streaming potential and some test applications.

We present a measurement cell that allows simultaneous measurement of second harmonic generation (SHG) and streaming potential (SP) at mineral-water interfaces with flat specimen that are suitable for non-linear optical (NLO) studies. The set-up directly yields SHG data for the interface of interest and can also be used to obtain information concerning the influence of flow on NLO signals from that interface. The streaming potential is at present measured against a reference substrate (PTFE). The properties of this inert reference can be independently determined for the same conditions. With the new cell, for the first time the SHG signal and the SP for flat surfaces have been simultaneousl…

Absolute acidity of clay edge sites from ab-initio simulations

International audience; We provide a microscopic understanding of the solvation structure and reactivity of the edges of neutral clays. In particular we address the tendency to deprotonation of the different reactive groups on the (0 1 0) face of pyrophyllite. Such information cannot be inferred directly from titration experiments, which do not discriminate between different sites and whose interpretation resorts to macroscopic models. The determination of the corresponding pKa then usually relies on bond valence models, sometimes improved by incorporating some structural information from ab-initio simulations. Here we use density functional theory based molecular dynamics simulations, comb…

Oberflächenladungen an der CaF 2 ‐Wasser‐Grenzfläche erlauben eine sehr schnelle intermolekulare Übertragung von Schwingungsenergie

Intrinsic Acidity of Surface Sites in Calcium Silicate Hydrates and Its Implication to Their Electrokinetic Properties

Calcium Silicate Hydrates (C–S–H) are the major hydration products of portland cement paste. The accurate description of acid–base reactions at the surface of C–S–H particles is essential for both understanding the ion sorption equilibrium in cement and prediction of mechanical properties of the hardened cement paste. Ab initio molecular dynamics simulations at the density functional level of theory were applied to calculate intrinsic acidity constants (pKa’s) of the relevant ≡SiOH and ≡CaOH2 groups on the C–S–H surfaces using a thermodynamic integration technique. Ion sorption equilibrium in C–S–H was modeled applying ab initio calculated pKa’s in titrating Grand Canonical Monte Carlo simu…

Liquid–solid interfaces: structure and dynamics from spectroscopy and simulations

Liquid–solid interfaces play an important role in a number of phenomena encountered in biological, chemical and physical processes. Surface-induced changes of the material properties are not only important for the solid support but also for the liquid itself. In particular, it is now well established that water at the interface is substantially different from bulk water, even in the proximity of apparently inert surfaces such as a simple metal. The complex chemistry at liquid–solid interfaces is typically fundamental to heterogeneous catalysis and electrochemistry, and has become especially topical in connection with the search for new materials for energy production. A quite remarkable exa…

Microscopic Insights into the Fluorite/Water Interfaces from Vibrational Sum Frequency Generation Spectroscopy

Water/mineral interfaces are central to a wide range of environmental and technological processes. In this report we provide a quantitative, molecular-level understanding of the CaF2/water interface using Density Functional Theory-based molecular dynamics simulations. In particular through the comparison of calculated Vibrational Sum Frequency Generation spectra to the experimental ones, we give a structural characterisation of the interface at different pH. At low pH, the surface is positively charged, causing a substantial degree of water ordering. Our results suggest that the surface charge originates from the dissolution of fluoride ions of the topmost layer, rather than from proton ads…

Lipid carbonyl groups terminate the hydrogen bond network of membrane-bound water.

We present a combined experimental sum-frequency generation (SFG) spectroscopy and ab initio molecular dynamics simulations study to clarify the structure and orientation of water at zwitterionic phosphatidylcholine (PC) lipid and amine N-oxide (AO) surfactant monolayers. Simulated O-H stretch SFG spectra of water show good agreement with the experimental data. The SFG response at the PC interface exhibits positive peaks, whereas both negative and positive bands are present for the similar zwitterionic AO interface. The positive peaks at the water/PC interface are attributed to water interacting with the lipid carbonyl groups, which act as efficient hydrogen bond acceptors. This allows the …

Effects of shear flow on the structure and dynamics of ionic liquids in a metallic nanoconfinement.

It has been shown that a weak shear can induce crystallisation in a disordered, glassy state. In this study, we use molecular dynamics simulations in order to investigate the out-of-equilibrium properties of [BMIM][BF4] confined between metal slabs. In particular, we want to understand the extent to which the shear flow modifies the interfacial properties. In particular, the questions we address here are (i) is the shear able to promote the crystalline phase in [BMIM][BF4]? (ii) Can, as a consequence of shear flow, a solid-like layer develop at the interface with a metallic surface? (iii) What are the tribological properties of nanoconfined [BMIM][BF4]? We find that the system behaves quite…

A Microscopic Interpretation of Pump–Probe Vibrational Spectroscopy Using Ab Initio Molecular Dynamics

What happens when extra vibrational energy is added to water? Using nonequilibrium molecular dynamics simulations, also including the full electronic structure, and novel descriptors, based on projected vibrational density of states, we are able to follow the flow of excess vibrational energy from the excited stretching and bending modes. We find that the energy relaxation, mostly mediated by a stretching-stretching coupling in the first solvation shell, is highly heterogeneous and strongly depends on the local environment, where a strong hydrogen bond network can transport energy with a time scale of 200 fs, whereas a weaker network can slow down the transport by a factor 2-3.

Enhanced Acid Dissociation at the Solid/Liquid Interface

In this chapter we review some recent results from first principles molecular dynamics simulations which show how molecular properties, such as proton dissociation, can be influenced upon adsorption at a solid/liquid interface. In particular, we discuss in details the increased acidity of pyruvic acid at the quartz /water interface, which is of relevance for the chemistry of the atmosphere. Our simulations unveil the special role of the microsolvation at interface, as well as the role of the silanols in stabliziing the deprotonated form of the acid. The enhanced acidity at the hydrophilic quartz/water interface is at odd with what typically found at the water/air interface where acidity is …

Atypical titration curves for GaAl12Keggin-ions explained by a joint experimental and simulation approach

Although they have been widely used as models for oxide surfaces, the deprotonation behaviors of the Keggin-ions (MeAl127+) and typical oxide surfaces are very different. On Keggin-ions, the deprotonation occurs over a very narrow pH range at odds with the broad charging curve of larger oxide surfaces. Depending on the Me concentration, the deprotonation curve levels off sooner (high Me concentration) or later (for low Me concentration). The leveling off shows the onset of aggregation before which the Keggin-ions are present as individual units. We show that the atypical titration data previously observed for some GaAl12 solutions in comparison to the originally reported data can be explain…

Dynamical heterogeneities of rotational motion in room temperature ionic liquids evidenced by molecular dynamics simulations

Room temperature ionic liquids (RTILs) have been shown to exhibit spatial heterogeneity or structural heterogeneity in the sense that they form hydrophobic and ionic domains. Yet studies of the relationship between this structural heterogeneity and the ∼picosecond motion of the molecular constituents remain limited. In order to obtain insight into the time scales relevant to this structural heterogeneity, we perform molecular dynamics simulations of a series of RTILs. To investigate the relationship between the structures, i.e., the presence of hydrophobic and ionic domains, and the dynamics, we gradually increase the size of the hydrophobic part of the cation from ethylammonium nitrate (EA…

Redox potentials and acidity constants from density functional theory based molecular dynamics.

CONSPECTUS: All-atom methods treat solute and solvent at the same level of electronic structure theory and statistical mechanics. All-atom computation of acidity constants (pKa) and redox potentials is still a challenge. In this Account, we review such a method combining density functional theory based molecular dynamics (DFTMD) and free energy perturbation (FEP) methods. The key computational tool is a FEP based method for reversible insertion of a proton or electron in a periodic DFTMD model system. The free energy of insertion (work function) is computed by thermodynamic integration of vertical energy gaps obtained from total energy differences. The problem of the loss of a physical refe…

Increased Acid Dissociation at the Quartz/Water Interface.

As shown by a quite significant amount of literature, acids at the water surface tend to be “less” acid, meaning that their associated form is favored over the conjugated base. What happens at the solid/liquid interface? In the case of the silica/water interface, we show how the acidity of adsorbed molecules can instead increase. Using a free energy perturbation approach in combination with electronic structure-based molecular dynamics simulations, we show how the acidity of pyruvic acid at the quartz/water interface is increased by almost two units. Such increased acidity is the result of the specific microsolvation at the interface and, in particular, of the stabilization of the deprotona…

Vibrational Sum Frequency Generation Spectroscopy of the Water Liquid–Vapor Interface from Density Functional Theory-Based Molecular Dynamics Simulations

International audience; The vibrational sum frequency generation (VSFG) spectrum of the water liquid-vapor (LV) interface is calculated using density functional theory-based molecular dynamics simulations. The real and imaginary parts of the spectrum are in good agreement with the experimental data, and we provide an assignment of the SFG bands according to the dipole orientation of the interfacial water molecules. We use an instantaneous definition of the surface, which is more adapted to the study of interfacial phenomena than the Gibbs dividing surface. By calculating the vibrational (infrared, Raman) properties for interfaces of varying thickness, we show that the bulk spectra signature…

Understanding the Acidic Properties of the Amorphous Hydroxylated Silica Surface

Amorphous silica is an intrinsic challenging system to study. In the last decades, some particular chemical properties have been discovered and described, but their description and understanding at the molecular level are experimentally difficult. Therefore, theoretical quantum chemical methods and descriptors, combined with experimental input, are a very appropriate set up to tackle this topic. In this study, the acidity of silanol groups of amorphous silica in hydrated conditions is investigated. Special attention has been drawn to the chemical shift, but also Bader charges, and vibrational frequencies with their intensities. The known bimodal acidity behavior was recovered and rationaliz…

Surface charges at the CaF2/water interface allow very fast intermolecular vibrational-energy transfer

Abstract We investigate the dynamics of water in contact with solid calcium fluoride, where at low pH, localized charges can develop upon fluorite dissolution. We use 2D surface‐specific vibrational spectroscopy to quantify the heterogeneity of the interfacial water (D2O) molecules and provide information about the sub‐picosecond vibrational‐energy‐relaxation dynamics at the buried solid/liquid interface. We find that strongly H‐bonded OD groups, with a vibrational frequency below 2500 cm−1, display very rapid spectral diffusion and vibrational relaxation; for weakly H‐bonded OD groups, above 2500 cm−1, the dynamics slows down substantially. Atomistic simulations based on electronic‐structu…

pKa at Quartz/Electrolyte Interfaces.

Acidity of silanol sites at the crystalline quartz/aqueous electrolyte (NaCl, NaI, KCl) interfaces are calculated from ab initio molecular dynamics simulations. pKa’s are found to follow a combination of the cationic and anionic Hofmeister series in the order pKa(neat solution) &lt; pKa(NaCl) &lt; pKa(NaI) &lt; pKa(KCl), in agreement with experimental measurements. Rationalization of this ranking is achieved in terms of the microscopic local solvation of the protonated silanols and their conjugated bases, the silanolates SiO–. The change in the pKa is the result of both water destructuring by alkali halides, as well as of the specific cation/SiO– interaction, depending on the electrolyte. M…

Hole Localization and Thermochemistry of Oxidative Dehydrogenation of Aqueous Rutile TiO2(110)

Trimesic acid on Cu in ethanol: Potential-dependent transition from 2-D adsorbate to 3-D metal-organic framework

We report the potential-dependent interactions of trimesic acid with Cu surfaces in EtOH. CV experiments and electrochemical surface-enhanced Raman spectroscopy show the presence of an adsorbed trimesic acid layer on Cu at potentials lower than 0 V vs Cu. The BTC coverage increases as the potential increases, reaching a maximum at 0 V. Based on molecular dynamics simulations, we report adsorption geometries and possible structures of the organic adlayer. We find that, depending on the crystal facet, trimesic acid adsorbs either flat or with one or two of the carboxyl groups facing the metal surface. At higher coverages, a multi-layer forms that is composed mostly of flat-lying trimesic acid…

Mineral-Water Interaction

Sum Frequency Generation Spectra from Velocity–Velocity Correlation Functions

We developed an expression for the calculation of the sum frequency generation spectra (SFG) of water interfaces that is based on the projection of the atomic velocities on the local normal modes. Our approach permits one to obtain the SFG signal from suitable velocity-velocity correlation functions, reducing the computational cost to that of the accumulation of a molecular dynamics trajectory, and therefore cutting the overhead costs associated with the explicit calculation of the dipole moment and polarizability tensor. Our method permits to interpret the peaks in the spectrum in terms of local modes, also including the bending region. The results for the water-air interface, obtained usi…

Role of pH in the synthesis and growth of gold nanoparticles using L-asparagine: a combined experimental and simulation study

Abstract The use of biomolecules as capping and reducing agents in the synthesis of metallic nanoparticles constitutes a promising framework to achieve desired functional properties with minimal toxicity. The system’s complexity and the large number of variables involved represent a challenge for theoretical and experimental investigations aiming at devising precise synthesis protocols. In this work, we use L-asparagine (Asn), an amino acid building block of large biomolecular systems, to synthesise gold nanoparticles (AuNPs) in aqueous solution at controlled pH. The use of Asn offers a primary system that allows us to understand the role of biomolecules in synthesising metallic nanoparticl…

Ab Initio Liquid Water Dynamics in Aqueous TMAO Solution

Ab initio molecular dynamics (AIMD) simulations in trimethylamine N-oxide (TMAO)-D2O solution are employed to elucidate the effects of TMAO on the reorientational dynamics of D2O molecules. By decomposing the O-D groups of the D2O molecules into specific subensembles, we reveal that water reorientational dynamics are retarded considerably in the vicinity of the hydrophilic TMAO oxygen (O(TMAO)) atom, due to the O-D···O(TMAO) hydrogen-bond. We find that this reorientational motion is governed by two distinct mechanisms: The O-D group rotates (1) after breaking the O-D···O(TMAO) hydrogen-bond, or (2) together with the TMAO molecule while keeping this hydrogen-bond intact. While the orientatio…